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Probing the Effects of Electron Deficient Aryl Substituents and a π‐System Extended NHC Ring on the Photocatalytic CO 2 Reduction Reaction with Re‐pyNHC‐Aryl Complexes **
Author(s) -
Shirley Hunter,
Sexton Thomas More,
Liyanage Nalaka P.,
Perkins Morgan A.,
Autry Shane A.,
McNamara Louis E.,
Hammer Nathan I.,
Parkin Sean R.,
Tschumper Gregory S.,
Delcamp Jared H.
Publication year - 2021
Publication title -
chemphotochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.13
H-Index - 18
ISSN - 2367-0932
DOI - 10.1002/cptc.202000296
Subject(s) - photocatalysis , aryl , photochemistry , dissociation (chemistry) , chemistry , ligand (biochemistry) , rhenium , excited state , substituent , polar effect , bond dissociation energy , electrochemistry , ring (chemistry) , homo/lumo , catalysis , medicinal chemistry , organic chemistry , molecule , atomic physics , electrode , biochemistry , alkyl , receptor , physics
The ever‐expanding need for renewable energy can be addressed in part by photocatalytic CO 2 reduction to give fuels via an artificial photosynthetic process driven by sunlight. A series of rhenium photocatalysts are evaluated in the photocatalytic CO 2 reduction reaction and via photophysical, electrochemical, and computational studies. The impact of various electron withdrawing substituents on the aryl group of the pyNHC‐aryl ligand along with the impact of extending conjugation along the backbone of the ligand is analyzed. A strong correlation between excited‐state lifetimes, photocatalytic rates, and computationally determined dissociation energy of the labile ligand of these complexes is observed. Additionally, computed orbital analysis provides an added understanding, which allows for prediction of the potential impact of an electron withdrawing substituent on photocatalysis.